Chlorine dioxide solution generator with temperature control capability

ABSTRACT

A chlorine dioxide solution generator includes a chlorine dioxide gas source and an absorption loop for effecting the dissolution of chlorine dioxide into a liquid stream. A gas transfer assembly is interposed between the chlorine dioxide gas source and the absorption loop. The gas transfer assembly includes a gas transfer pump and an exhaust manifold assembly. The exhaust manifold assembly includes a manifold conduit defining an interior volume for directing the pressurized chlorine dioxide gas stream from the pump outlet to the absorption loop. The manifold conduit interior volume is sufficiently large to inhibit chlorine dioxide decomposition in the pressurized chlorine dioxide gas stream by induce a pressurized chlorine dioxide gas stream temperature within the manifold conduit of less than about 163° F. (73° C.).

CROSS-REFERENCE TO RELATED APPLICATION(S)

This application is a continuation-in-part of U.S. patent applicationSer. No. 10/902,681 filed on Jul. 29, 2004, entitled “Chlorine DioxideSolution Generator”. The '681 application is hereby incorporated byreference herein in its entirety.

FIELD OF THE INVENTION

The present invention relates generally to chlorine dioxide generatorsand to the use of such generators in water treatment systems. Moreparticularly, the present invention relates to a chlorine dioxidegenerator for producing a chlorine dioxide solution, in which thetemperature of the chlorine dioxide stream is controlled to reduce oravoid decomposition of chlorine dioxide in the stream.

BACKGROUND OF THE INVENTION

Chlorine dioxide (ClO₂) has many industrial and municipal uses. Whenproduced and handled properly, ClO₂ is an effective and powerfulbiocide, disinfectant and oxidizer.

ClO₂ is also used extensively in the pulp and paper industry as ableaching agent, but is gaining further support in such areas asdisinfections in municipal water treatment. Other end-uses can includeas a disinfectant in the food and beverage industries, wastewatertreatment, industrial water treatment, cleaning and disinfections ofmedical wastes, textile bleaching, odor control for the renderingindustry, circuit board cleansing in the electronics industry, and usesin the oil and gas industry.

In water treatment applications, ClO₂ is primarily used as adisinfectant for surface waters with odor and taste problems. It is aneffective biocide at low concentrations and over a wide pH range. ClO₂is desirable because when it reacts with an organism in water, chloriteresults, which studies to date have shown does not pose a significantadverse risk to human health. The use of chlorine, on the other hand,can result in the creation of chlorinated organic compounds whentreating water. Such chlorinated organic compounds are suspected toincrease cancer risk.

Producing ClO₂ gas for use in a ClO₂ water treatment process isdesirable because there is greater assurance of ClO₂ purity when in thegas phase. ClO₂ is, however, unstable in the gas phase and will readilyundergo decomposition into chlorine gas (C1₂), oxygen gas (O₂), andheat. The high reactivity of ClO₂ generally requires that it be producedand used at the same location. ClO₂ is, however, soluble and stable inan aqueous solution.

The production of ClO₂ can be accomplished both by electrochemical andreactor-based chemical methods. Electrochemical methods have anadvantage of relatively safer operation compared to reactor-basedchemical methods. In this regard, electrochemical methods employ onlyone precursor, namely, a chlorite solution, unlike the multipleprecursors that are employed in reactor-based chemical methods.Moreover, in reactor-based chemical methods, the use of concentratedacids and chlorine gas poses a safety concern.

Electrochemical cells are capable of carrying out selective oxidationreaction of chlorite to ClO₂ The selective oxidation reaction product isa solution containing ClO₂. To further purify the ClO₂ gas stream, thegas stream is separated from the solution using a stripper column. Inthe stripper column, air is passed from the bottom of the column to thetop while the ClO₂ solution travels from top to the bottom. Pure ClO₂ isexchanged from solution to the air. Suction of air is usuallyaccomplished using an eductor, as described in copending and co-ownedapplication Ser. No. 10/902,681, of which the present application is acontinuation-in-part.

As described in the '681 application, ClO₂ can be prepared a number ofways, generally via a reaction involving either chlorite (ClO₂—) orchlorate (ClO₃—) solutions. The ClO₂ created through such a reaction isoften refined to generate ClO₂ gas for use in the water treatmentprocess. The ClO₂ gas is then educed into the water selected fortreatment. Eduction occurs where the ClO₂ gas, in combination with air,is mixed with the water selected for treatment.

As further described in the '681 application, for many water treatmentsystems, the eduction process is effective to introduce ClO₂ gasdirectly into the process water. An operational problem can occur,however, when air is simultaneously introduced into a water system whileeducing the ClO₂ gas. A significant corrosion potential results fromoxygen in air being added into the system.

Another problem can occur when introducing ClO₂ gas into a pressurizedwater system. Treating water in pressurized systems can be difficultwhen using educed ClO₂ gas, since high-pressure booster pumps may beneeded along with high-performance eductors. This not only increasescost, but also raises maintenance concerns, since high-performanceeduction systems can be unreliable as operating pressures near or above30 to 50 pounds per square inch (psi) (206.8 to 344.7 kilopascal (kPa)).

The foregoing eductor-based method is less effective, however, insystems in which a ClO₂ stream is directed against a head pressure. Toovercome this deficiency, a vacuum gas transfer pump can be employedinstead of the eductor described in the '681 application. The size andcapacity of the vacuum gas transfer pump are preferably determined byparameters associated with safe, efficient and reliable operation of thegenerator. In this regard, it has been determined that, for safe,efficient and reliable operation of the generator, a ClO₂ concentrationof less than about 10 percent by volume of a stream comprising ClO₂ inair, the lower decomposition limit, is preferred. To further increasethe safety margin of the generator, a ClO₂ concentration of less thanabout 5 percent by volume of a stream comprising ClO₂ in air is moredesirable.

As the amount of ClO₂ produced by the generator increases, the amount ofair required for the effective operation of the stripper column alsoincreases. The production range of the generator therefore determinesthe size of the vacuum gas transfer pump. As the pump size increase thevelocity of the mixed air/ClO₂ stream exiting the pump increases.Consequently, the temperature of the gas mixture increases.

It is known that ClO₂ is unstable and capable of decomposing, in whichClO₂ undergoes an exothermic reaction to form chlorine and oxygen. Infact, and as described in more detail below, an operating temperaturegreater than about 163° F. (73° C.) can result in potentially hazardousand less efficient operation of the generator. In the present technique,in which the ClO₂ solution generator has temperature control capability,the operating temperature can be reduced and maintained below the levelat which the exothermic reaction to form chlorine and oxygen causes theClO₂ generation process to become hazardous and less efficient.

SUMMARY OF THE INVENTION

A chlorine dioxide solution generator comprises a ClO₂ gas source, anabsorption loop for effecting the dissolution of ClO₂ into a liquidstream, the absorption loop fluidly connected to the ClO₂ gas source,and a gas transfer assembly interposed between the ClO₂ gas source andthe absorption loop. The gas transfer assembly comprises:

-   -   (1) a gas transfer pump having at least one inlet port for        receiving a ClO₂ gas stream from the ClO₂ gas source and at        least one outlet port for discharging a pressurized ClO₂ gas        stream; and    -   (2) an exhaust manifold assembly extending from the at least one        gas transfer pump outlet port.        The exhaust manifold assembly comprises at least one manifold        conduit defining an interior volume for directing the        pressurized ClO₂ gas stream from the at least one gas transfer        pump outlet port to the absorption loop. The at least one        manifold conduit interior volume is sufficiently large to        inhibit ClO₂ decomposition in the pressurized ClO₂ gas stream.

In a preferred chlorine dioxide solution generator, the at least onemanifold conduit interior volume is sufficiently large to induce apressurized ClO₂ gas stream temperature within the at least one manifoldconduit of less than about 163° F. (73° C.).

In a preferred chlorine dioxide solution generator, the gas transferpump has first and second inlet ports for receiving first and secondClO₂ gas streams from the ClO₂ gas source. The gas transfer pump hasfirst and second outlet ports for discharging first and secondpressurized ClO₂ gas streams. The discharge manifold assembly comprisesfirst and second manifold conduits defining an aggregate conduitinterior volume for directing the first and second pressurized ClO₂ gasstreams, respectively, from the gas transfer pump to the absorptionloop. The aggregate manifold conduit interior volume is sufficientlylarge to inhibit ClO₂ decomposition in the pressurized ClO₂ gas stream.

In a preferred chlorine dioxide solution generator, the first and secondinlet ports each has an inlet port conduit extending therefrom forreceiving first and second ClO₂ gas streams from the ClO₂ gas source.The first and second outlet ports each has an outlet port conduitextending therefrom for discharging first and second pressurized ClO₂gas streams. The exhaust manifold assembly comprises first and secondmanifold conduits defining an aggregate conduit interior volume fordirecting the first and second pressurized ClO₂ gas streams,respectively, from the gas transfer pump to the absorption loop. Theaggregate manifold conduit interior volume is sufficiently large toinhibit ClO₂ decomposition in the pressurized ClO₂ gas stream.

In a preferred chlorine dioxide solution generator, the first and secondinlet ports each has an inlet port conduit extending therefrom forreceiving first and second ClO₂ gas streams from the ClO₂ gas source.The first and second outlet ports each has a pair of outlet portconduits extending therefrom for discharging two pairs of pressurizedClO₂ gas streams. The exhaust manifold assembly comprises at least onemanifold conduit defining an aggregate conduit interior volume fordirecting the first and second pressurized ClO₂ gas streams,respectively, from the gas transfer pump to the absorption loop. Theaggregate manifold conduit interior volume is sufficiently large toinhibit ClO₂ decomposition in the pressurized ClO₂ gas stream. Theexhaust manifold assembly preferably comprises a single manifold conduitdefining an interior volume for directing the two pairs of pressurizedClO₂ gas streams from the gas transfer pump to the absorption loop. Theinterior volume is sufficiently large to inhibit ClO₂ decomposition inthe pressurized ClO₂ gas stream.

In preferred embodiments of the chlorine dioxide solution generator, theoutlet port conduits are preferably formed from a material selected fromthe group consisting of polytetrafluoroethylene (PTFE; commerciallyavailable from DuPont under the trade name Teflon®,polychlorotrifluoroethylene, chlorinated poly(vinyl chloride), titaniumand other metals having a melting point greater than about 140° F. (60°C.).

In preferred embodiments of the chlorine dioxide solution generator, aratio of the cross-sectional diameter of the at least one manifoldconduit to the cross-sectional diameter of the at least one gas transferpump outlet port is greater than 1.

In preferred embodiments of the chlorine dioxide solution generator, theexhaust manifold assembly has a coolant fluid stream in thermal contacttherewith. In operation, the coolant fluid stream further inhibits ClO₂decomposition in the pressurized ClO₂ gas stream. The coolant fluidstream is preferably in thermal contact with the at least one manifoldconduit. The thermal contact of the coolant fluid stream with the atleast one manifold conduit further induces a pressurized ClO₂ gas streamtemperature within the at least one manifold conduit of less than about163° F. (73° C.).

A method of generating a chlorine dioxide solution comprises:

-   -   (a) providing a source of ClO₂ gas;    -   (b) effecting the dissolution of ClO₂ into a liquid stream by        employing an absorption loop fluidly connected to the ClO₂ gas        source;    -   (c) interposing a gas transfer pump between the ClO₂ gas source        and the absorption loop, the gas transfer pump having at least        one inlet port for receiving a ClO₂ gas stream from the ClO₂ gas        source and at least one outlet port for discharging a        pressurized ClO₂ gas stream;    -   (d) interposing an exhaust manifold assembly between the gas        transfer pump outlet port and the absorption loop, the exhaust        manifold assembly comprising at least one manifold conduit        defining an interior volume for directing the pressurized ClO₂        gas stream from the at least one gas transfer pump outlet port        to the absorption loop; and    -   (e) inhibiting ClO₂ decomposition in the pressurized ClO₂ gas        stream by effecting a volumetric increase between the at least        one gas transfer pump outlet port and the at least one manifold        conduit.

In a preferred embodiments of the method, the volumetric increaseinduces a pressurized ClO₂ gas stream temperature within the at leastone manifold conduit of less than about 163° F. (73° C.).

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a process flow diagram of a ClO₂ solution generator of thetype described in application Ser. No. 10/902,681.

FIG. 2 is a process flow diagram of an anolyte loop of a ClO₂ solutiongenerator of the type described in the '681 application.

FIG. 3 is a process flow diagram of a catholyte loop of a ClO₂ solutiongenerator of the type described in the '681 application.

FIG. 4 is a process flow diagram of an absorption loop of a ClO₂solution generator of the type described in the '681 application.

FIG. 5 a is a top view of a ClO₂ gas stream pump configuration in a ClO₂solution generator, but without the temperature control capability ofthe present technique.

FIG. 5 b is a top view of a first embodiment of a ClO₂ gas stream pumpconfiguration for a ClO₂ solution generator having temperature controlcapability.

FIG. 5 c is a top view of a second embodiment of a ClO₂ gas stream pumpconfiguration for a ClO₂ solution generator having temperature controlcapability.

FIG. 6 is a top view of an embodiment of a ClO₂ gas stream pumpconfiguration for a ClO₂ solution generator having temperature controlcapability, similar to the embodiment illustrated in FIG. 5 b, but inwhich a water stream is mixed with the ClO₂ stream to further controlthe temperature of the ClO₂ stream before introducing the mixed streamto the absorption loop.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENT(S)

FIG. 1 illustrates a process flow diagram of an embodiment of chlorinedioxide solution generator 100 of the type described in application Ser.No. 10/902,681. The process flow of FIG. 1 consists of threesub-processes including an anolyte loop 102, a catholyte loop 104, andan absorption loop 106. The purpose of anolyte loop 102 is to produce aClO₂ gas by oxidation of chlorite, and the process can be referred to asa ClO₂ gas generator loop. The ClO₂ gas generator loop is essentially aClO₂ gas source. Various sources of ClO₂ are available and known in thewater treatment field. Catholyte loop 104 of the ClO₂ gas generator loopproduces sodium hydroxide and hydrogen gas by reduction of water. Oncethe ClO₂ gas is produced in the ClO₂ gas generator loop, the ClO₂ gas istransferred to absorption loop 106 where the gas is further conditionedfor water treatment end-uses. The process can be operated through aprogram logic control (PLC) system 108 that can include visual and/oraudible displays.

In this application, the term “absorb” refers to the process ofdissolving or infusing a gaseous constituent into a liquid, optionallyusing pressure to effect the dissolution or infusion. Here, ClO₂ gas,which is produced in the ClO₂ gas generator loop, is “absorbed” (thatis, dissolved or infused) into an aqueous liquid stream directed throughabsorption loop 106.

FIG. 2 illustrates an anolyte loop 102 in an embodiment of chlorinedioxide solution generator 100 of the type described in the '681application. The contribution of anolyte loop 102 to the ClO₂ solutiongenerator is to produce a ClO₂ gas that is directed to absorption loop106 for further processing. Anolyte loop 102 embodiment of FIG. 2 is fora ClO₂ gas produced using a reactant feedstock 202. In a preferredembodiment, a 25 percent by weight sodium chlorite (NaClO₂) solution canbe used as reactant feedstock 202. However, feedstock concentrationsranging from 0 percent to a maximum solubility (40 percent at 17° C. inthe embodiment involving NaClO₂), or other suitable method of injectingsuitable electrolytes, can be employed.

The reactant feedstock 202 is connected to a chemical metering pump 204,which delivers the reactant feedstock 202 to a recirculating connection206 in the anolyte loop 102. Recirculating connection 206 in anolyteloop connects a stripper column 208 to an electrochemical cell 210. Thedelivery of the reactant feedstock 202 can be controlled using PLCsystem 108. PLC system 108 can be used to activate chemical meteringpump 204 according to signals received from a pH sensor 212. pH sensor212 is generally located along recirculating connection 206. A pH setpoint can be established in PLC system 108, and once the set point isreached, the delivery of reactant feedstock 202 can either start orstop.

Reactant feedstock 202 is delivered to a positive end 214 ofelectrochemical cell 210 where the reactant feedstock is oxidized toform a ClO₂ gas, which is then dissolved in an electrolyte solutionalong with other side products. The ClO₂ solution with the side productsis directed away from electrochemical cell 210 to the top of strippercolumn 208 where a pure ClO₂ is stripped off in a gaseous form from theother side products. Side products or byproducts can include chlorine,chlorates, chlorites and/or oxygen. The pure ClO₂ gas is then removedfrom stripper column 208 under a vacuum induced by gas transfer pump216, or analogous gas or fluid transfer device (such as, for example, avacuum-based device), where it is delivered to adsorption loop 106. Theremaining solution is collected at the base of stripper column 208 andrecirculated back across the pH sensor 212 where additional reactantfeedstock 202 can be added. The process with the reactant feedstockand/or recirculation solution being delivered into positive end 214 ofelectrochemical cell 210 is then repeated.

As described in the '681 application, modifications to the anolyte loopprocess can be made that achieve similar results. As an example, ananolyte hold tank can be used in place of a stripper column. In such acase, an inert gas or air can be blown over the surface or through thesolution to separate the ClO₂ gas from the anolyte. As another example,chlorate can be reduced to produce ClO₂ in a cathode loop instead ofchlorite. The ClO₂ gas would then similarly be transferred to theabsorption loop. In a further example, ClO₂ can be generated by purelychemical generators and transferred to an absorption loop for furtherprocessing.

FIG. 3 illustrates a catholyte loop 104 in an embodiment of a chlorinedioxide solution generator 100 of the type described in the '681application. Catholyte loop 104 contributes to the chlorine dioxidesolution generator 100 by handling byproducts produced from theelectrochemical reaction of reactant feedstock 202 solution in anolyteloop 102. As an example, where a sodium chlorite (NaClO₂) solution isused as reactant feedstock 202, sodium ions from the anolyte loop 102migrate to catholyte loop 104 through a cationic membrane 302, inelectrochemical cell 210, to maintain charge neutrality. Water in thecatholyte is reduced to produce hydroxide and hydrogen (H₂) gas. Theresulting byproducts in catholyte loop 104, in the example of an NaClO₂reactant feedstock, are sodium hydroxide (NaOH) and hydrogen gas. Thebyproducts are directed to a byproduct tank 304.

In an embodiment of catholyte loop 104 in the example of a NaClO₂reactant feedstock, a soft (that is, demineralized) water source 306 canbe used to dilute the byproduct NaOH using a solenoid valve 308connected between soft water source 306 and the byproduct tank 304.Solenoid valve 308 can be controlled with PLC system 108. In a preferredembodiment, PLC system 108 can use a timing routine that maintains theNaOH concentration in a range of 5 percent to 20 percent. When byproducttank 304 reaches a predetermined level above the base of byproduct tank304, the diluted NaOH byproduct above that level is removed fromcatholyte loop 104.

In the example of a NaClO₂ reactant feedstock, catholyte loop 104 selfcirculates using the lifting properties of the H₂ byproduct gas formedduring the electrochemical process and forced water feed from soft watersource 306. The H₂ gas rises up in byproduct tank 304 where there is ahydrogen disengager 310. The H₂ gas can be diluted with air in hydrogendisengager 310 to a concentration of less than 0.5 percent. The dilutedH₂ gas can be discharged from catholyte loop 104 and chlorine dioxidesolution generator 100 using a blower 312.

As described in the '681 application, in another embodiment, dilutesodium hydroxide can be fed instead of water to produce concentratedsodium hydroxide. Oxygen or air can also be used as a reductant insteadof water to reduce overall operation voltage since oxygen reduces atlower voltage than water.

The reaction of anolyte loop 102 and catholyte loop 104 in theembodiment illustrated in FIGS. 2 and 3 is represented by the followingnet chemical equation:2NaClO_(2(aq))+2H₂O→2ClO_(2(gas))+2NaOH_((aq))+H_(2(gas))The NaClO₂ is provided by reactant feedstock 202 of anolyte loop 102.The NaOH and H₂ gas are byproducts of the reaction in catholyte loop104. The ClO₂ solution along with the starting unreacted NaClO₂ andother side products are directed to the stripper column for separatinginto ClO₂ gas as part of anolyte loop 102 process. Chlorite salts otherthan NaClO₂ can be used in anolyte loop 102.

FIG. 4 illustrates an absorption loop 106 of an embodiment of a chlorinedioxide solution generator 100 of the type described in the '681application. Absorption loop 106 processes the ClO₂ gas from anolyteloop 102 into a ClO₂ solution that is ready to be directed to the waterselected for treatment.

ClO₂ gas is removed from stripper column 208 of anolyte loop 102 usinggas transfer pump 216. In a preferred embodiment, a gas transfer pump216 can be used that is “V” rated at 75 Torr (10 kPa) with a dischargerate of 34 liters per minute. The vacuum and delivery rate of gastransfer pump 216 can vary depending upon the free space in strippercolumn 208 and desired delivery rate of ClO₂ solution.

The ClO₂ gas removed from stripper column 208 using gas transfer pump216 is directed to an absorber tank 402 of absorption loop 106. In apreferred embodiment, discharge side 404 of gas transfer pump 216delivers ClO₂ gas into a 0.5-inch (13-mm) poly(vinyl chloride) (PVC)injection line 406 external to absorber tank 402. Injection line 406 isan external bypass for fluid between the lower to the upper portions ofthe absorption tank 402. A gas injection line can be connected toinjection line 406 using a T-connection 408. Before ClO₂ gas is directedto absorber tank 402, the tank 402 is filled with water to approximately0.5 inch (13 mm) below a main level control 410. Main level control 410can be located below where injection line 406 connects to the upperportion of absorption tank 402. Introducing ClO₂ gas into injection line406 can cause a liquid lift that pushes newly absorbed ClO₂ solution uppast a forward-only flow switch 412 and into absorber tank 402. Flowswitch 412 controls the amount of liquid delivered to absorber tank 402.Absorber tank 402 has a main control level 410 to maintain a proper tanklevel. In addition to main control level 410, safety control levels canbe employed to maintain a high level 414 and low level 416 of liquidwhere main control level 410 fails. A process delivery pump 418 feedsClO₂ solution from absorption tank 402 to the end process withoutincluding air or other gases. Process delivery pump 418 is sized todeliver a desired amount of water per minute. The amount of ClO₂ gasdelivered to absorber tank 402 is set by the vacuum and delivery rateset by gas transfer pump 216.

PLC system 108 can provide a visual interface for the operator tooperate the entire chlorine dioxide solution generator 100. PLC system108 can automatically control the continuous operation and safety of theproduction of ClO₂ solution. PLC system 108 can set flow rates foranolyte loop 102 and catholyte loop 104. The safety levels of absorbertank 402 can also be enforced by PLC system 108. PLC system 108 can alsocontrol the power for achieving a desired current in an embodiment usingan electrochemical cell 210. In a preferred embodiment, the currentranges from 0 to 100 amperes, although currents higher than this averageare possible. The amount of current determines the amount of ClO₂ gasthat is produced in anolyte loop 102. The current of the power supplycan be determined by the amount of ClO₂ that is to be produced. PLCsystem 108 can also be used to monitor the voltage of electrochemicalcell 210. In a preferred embodiment, electrochemical cell 210 can beshut down when the voltage exceeds a safe voltage level. In anotherpreferred embodiment, 5 volts can be considered a safe voltage level.

As described in the '681 application, another operation that can bemonitored with PLC system 108 is the temperature of electrochemical cell210. If overheating occurs, PLC system 108 shuts down electrochemicalcell 210. PLC system 108 can also monitor the pH of the anolyte using apH sensor 212 (shown in FIG. 2). During operation of electrochemicalcell 210, the pH of the solution circulating in anolyte loop 102decreases as hydrogen ions are generated. In the exemplary embodiment ofthe NaClO₂ reactant feedstock, when the pH goes below 5, additionalreactant feedstock is added using PLC system 108. Control of pH can alsobe handled by adding a reactant that decreases the pH when pH may is toohigh.

As further described in the '681 application, in another embodiment, thetransfer line from gas transfer pump 216 can be connected to absorbertank 402 directly without injection line 406, and can allow forincreasing the transfer rate of the pump. Other embodiments can includea different method of monitoring the liquid level in absorber tank 402.For example, an oxidation and reduction potential (ORP) can be dipped inabsorber tank 402. ORP can be used to monitor the concentration of ClO₂in the solution in absorber tank 402. PLC system 108 can be used to seta concentration level for the ClO₂ as monitored by ORP, which providesan equivalent method of controlling the liquid level in absorber tank402. Optical techniques such as photometers can also be used to controlthe liquid level in absorber tank 402. Absorption loop 106 can be a partof the chlorine dioxide solution generator or it can be installed as aseparate unit outside of the chlorine dioxide solution generator. Inanother embodiment, process water can be fed directly in absorber tank402 and treated water can be removed from the absorber tank 402. Theprocess water can include a demineralized, or soft, water source 420 andthe process water feed can be controlled using a solenoid valve 422.

The process flow illustrated in FIGS. 1, 2 and 3 of the '681 applicationare based on ClO₂ gas produced using electrochemical cells and a sodiumchlorite solution. ClO₂ gas can be made using many different processesthat would be familiar to a person skilled in water treatmenttechnologies. Such processes include, but are not limited to,acidification of chlorite, oxidation of chlorite by chlorine, oxidationof chlorite by persulfate, use of acetic anhydride on chlorite, use ofsodium hypochlorite and sodium chlorite, use of dry chlorine/chlorite,reduction of chlorates by acidification in the presence of oxalic acid,reduction of chlorates by sulfur dioxide, and the ERCO R-2®, R-3®, R-5®,R-8®, R-10® and R-11® processes.

It has been determined that the material, the diameter, as well as therelative configuration and arrangement of the conduits (or pipes ortubes) associated with the present chlorine dioxide solution generatorare important for safe, efficient and reliable operation of thegenerator. In particular, the ClO₂ gas stream should be removed thegenerator at temperature greater than about 163° F. (73° C.) , dependingupon the diameter of the conduit or tube through which the ClO₂ gasstream is carried.

As previously stated, it is known that ClO₂ at a temperature greaterthan about 163° F. (73° C.) can decompose to form chlorine and oxygen.Such decomposition is typically accompanied by an increase in thetemperature of the ClO₂ stream, with temperatures as high 280° F. (138°C.), which is greater than the melting temperature of both PVC and CPVC(chlorinated poly(vinyl chloride)). PVC and CPVC are the typicalmaterials from which the fluid stream conduits or pipes employed inchlorine dioxide solution generators, and the melting of those conduitscan create hazardous operating conditions. It is therefore important toreduce and maintain the temperature of the chloride dioxide streamexiting the generator as low as possible.

FIG. 5 a shows a ClO₂ gas stream pump configuration 501 in a ClO₂solution generator, but without the temperature control capability ofthe present technique. Pump configuration 501 is interposed between aClO₂ gas source of the type illustrated in FIGS. 1 and 2, and anabsorption loop of the type illustrated in FIGS. 1 and 4.

Pump configuration 501 includes a gas transfer pump 510 interposedbetween an inlet manifold assembly 505 and an exhaust manifold assembly506. Gas transfer pump 510 has two head portions 512 a and 512 b, whichproduce a pressurized gas stream from an incoming gas stream. A ClO₂ gasstream from a ClO₂ gas source (not shown) is directed to pump 510 viaconduit 520, which branches at T-connector 524 to a pair of inletconduits 522 a, 522 b. The ClO₂ gas stream in inlet conduit 512 a is fedto pump head 512 a, where the stream is pressurized and discharged frompump head 512 a via outlet conduit 532 a. Similarly, the ClO₂ gas streamin inlet conduit 512 b is fed to pump head 512 b, where the stream ispressurized and discharged from pump head 512 b via outlet conduit 532b. The pressurized ClO₂ gas streams directed through outlet conduits 532a, 532 b are combined into one stream at T-connector 534, and thecombined stream is then directed through conduit 533 to a fitting 536,in which a thermocouple 537 is mounted and from which the combinedstream is directed to the absorption loop (not shown) via conduit 539and intermediate pipe connections and fittings, one of which isillustrated in FIG. 5 a as elbow fitting 538.

FIG. 5 b shows an embodiment of a ClO₂ gas stream pump configuration 502for a ClO₂ solution generator having temperature control capability. Aswith pump configuration 501 in FIG. 5 a, pump configuration 502 isinterposed between a ClO₂ gas source of the type illustrated in FIGS. 1and 2, and an absorption loop of the type illustrated in FIGS. 1 and 4.

Pump configuration 502 includes gas transfer pump 510, an inlet manifoldassembly 505, which as illustrated in FIG. 5 b is essentially identicalto the inlet manifold assembly shown in FIG. 5 a. Pump configuration 502also includes an exhaust manifold assembly 507, in which the inletstreams are pressurized and discharged from pump heads 512 a, 512 b viaoutlet conduits 532 a, 532 b, respectively. The pressurized ClO₂ gasstreams directed through outlet conduits 532 a, 532 b are separatelydirected to conduits in which the pressurized streams undergo volumetricexpansion. Thus, the pressurized ClO₂ gas stream in outlet conduit 532 ais directed to and expanded within a T-connector 546, and thepressurized ClO₂ gas stream in outlet conduit 532 b is directed to anelbow fitting 542, in which a thermocouple 537 is mounted and from whichthe stream is directed through conduit 544. The stream directed throughconduit 544 is combined with the other pressurized and expanded ClO₂ gasstream at T-connector 546, and the combined stream is then directed fromT-connector 546 to the downstream absorption loop via conduit 548 (andintermediate pipe connections and fittings, if any (not shown in FIG. 5b)).

FIG. 5 c shows an embodiment of a ClO₂ gas stream pump configuration 503for a ClO₂ solution generator having temperature control capability. Aswith pump configuration 501 in FIG. 5 a and pump configuration 502 inFIG. 5 b, pump configuration 503 is interposed between a ClO₂ gas sourceof the type illustrated in FIGS. 1 and 2, and an absorption loop of thetype illustrated in FIGS. 1 and 4.

Pump configuration 503 includes gas transfer pump 510, an inlet manifoldassembly 505, which as illustrated in FIG. 5 c is essentially identicalto the inlet manifold assembly shown in FIGS. 5 a and 5 b. Pumpconfiguration 503 also includes an exhaust manifold assembly 508, inwhich the inlet streams are pressurized and discharged from pump head512 a via outlet conduits 552 a, 552 b and from pump head 512 b viaoutlet conduits 552 c, 552 d. The pressurized ClO₂ gas streams directedthrough outlet conduits 552 a, 552 b, 552 c, 552 d are separatelydirected to a single conduit 554, in which the pressurized streams arecombined and undergo volumetric expansion. The stream directed throughconduit 554 is then directed to the downstream absorption loop (notshown) via conduit 558 (and intermediate pipe connections and fittings,if any). Thermocouples 557 a, 557 b are mounted on opposite ends ofconduit 544.

FIG. 6 shows a ClO₂ gas stream pump configuration 504 for a chlorinedioxide solution generator having temperature control capability, whichis similar to the embodiment illustrated in FIG. 5 b, but in which awater stream directed through conduit 559 is mixed with a pressurizedClO₂ gas stream to control the temperature of the ClO₂ stream(s) beforeintroducing the mixed stream(s) to the absorption loop.

EXAMPLE 1

The ClO₂ gas stream exiting the pump orifice in FIGS. 5 a, 5 b and 5 c,which has a diameter of 0.25 inch (0.64 cm) can be cooled by expandingthe volume of the gas stream. The extent of expansion should be suchthat the induction period for decomposition of ClO₂ at the temperatureand pressure indicated is greater than 20 seconds. According topublished graphs in the technical literature (see, for example, LossPrevention Bulletin, I. Chem. E. 113, October 1993 by G. Cowley), thetemperature and induction period for 5 percent by volume of ClO₂ in air(corresponds to a partial pressure of 38 mm of Hg) shown in Table 1below. TABLE 1 Induction period to decomposition of ClO₂ (5% by volumein air) at a partial pressure of 38 mm Hg Temperature Induction Period(° F./° C.) (minutes) 163/73 0.33 124/51 60 106/41 400

In the present chlorine dioxide solution generator with temperaturecontrol capability, the ClO₂ temperature is preferably reduced to andmaintained at below 163° F. (73° C.). This can be accomplished inseveral ways, as illustrated with reference to the embodiments of FIGS.5 a, 5 b and 5 c. The temperatures of the pressurized ClO₂ gas streamswere measured at thermocouple 537 (in the embodiment of FIG. 5 a), atthermocouple 543 (in the embodiment of FIG. 5 b), and at thermocouple557 b (in the embodiment of FIG. 5 c). The operating data is shown inTable 2 below. TABLE 2 Temperature of ClO₂ for various nominal diametersof the conduits depicted in FIGS. 5a, 5b and 5c Conduit 532a 532b 532c532d 533 539 544 554 Temp (in/ (in/ (in/ (in/ (in/ (in/ (in/ (in/ (° F./FIG. cm) cm) cm) cm) cm) cm) cm) cm) ° C.) 5a 0.50/ 0.50/ — — 0.50/1.00/ — — >280/ 1.27 1.27 1.27 2.54 >138 5b 0.50/ 0.50/ — — — — 1.00/ — 162/ 1.27 1.27 2.54  72 5b 0.75/ 0.75/ — — — — 2.00/ —  153/ 1.91 1.915.08  67 5b 0.75/ 0.75/ — — — — 1.00/ —  151/ 1.91 1.91 2.54  66 5c0.50/ 0.50/ 0.50/ 0.50/ — — — 2.00/  153/ 1.27 1.27 1.27 1.27 5.08  67

The data in Table 2 show that increasing the diameter of the conduitcarrying the ClO₂ stream induces a reduction in the temperature of thestream.

Another way of reducing the temperature of the ClO₂ stream is tointroduce water at the conduit, such as, for example, the conduit formedin T-connector 541 shown in FIG. 6, in which a water stream is mixedwith the ClO₂ stream to control the temperature of the ClO₂ streambefore introducing the mixed stream to the vacuum gas transfer pump.

While particular elements, embodiments and applications of the presentinvention have been shown and described, it will be understood, ofcourse, that the invention is not limited thereto since modificationscan be made by those skilled in the art without departing from the scopeof the present disclosure, particularly in light of the foregoingteachings.

1. A chlorine dioxide solution generator comprising: (a) a chlorinedioxide gas source; (b) an absorption loop for effecting the dissolutionof chlorine dioxide into a liquid stream, said absorption loop fluidlyconnected to said chlorine dioxide gas source; and (c) a gas transferassembly interposed between said chlorine dioxide gas source and saidabsorption loop, said gas transfer assembly comprising: (1) a gastransfer pump having at least one inlet port for receiving a chlorinedioxide gas stream from said chlorine dioxide gas source and at leastone outlet port for discharging a pressurized chlorine dioxide gasstream; and (2) an exhaust manifold assembly extending from said atleast one gas transfer pump outlet port, said exhaust manifold assemblycomprising at least one manifold conduit defining an interior volume fordirecting said pressurized chlorine dioxide gas stream from said atleast one gas transfer pump outlet port to said absorption loop, whereinsaid at least one manifold conduit interior volume is sufficiently largeto inhibit chlorine dioxide decomposition in said pressurized chlorinedioxide gas stream.
 2. The chlorine dioxide solution generator of claim1 wherein said at least one manifold conduit interior volume issufficiently large to induce a pressurized chlorine dioxide gas streamtemperature within said at least one manifold conduit of less than about163° F. (73° C.).
 3. The chlorine dioxide solution generator of claim 1wherein said gas transfer pump has first and second inlet ports forreceiving first and second chlorine dioxide gas streams from saidchlorine dioxide gas source, wherein said gas transfer pump has firstand second outlet ports for discharging first and second pressurizedchlorine dioxide gas streams, and wherein said discharge manifoldassembly comprises first and second manifold conduits defining anaggregate conduit interior volume for directing said first and secondpressurized chlorine dioxide gas streams, respectively, from said gastransfer pump to said absorption loop, wherein said aggregate manifoldconduit interior volume is sufficiently large to inhibit chlorinedioxide decomposition in said pressurized chlorine dioxide gas stream.4. The chlorine dioxide solution generator of claim 3 wherein saidaggregate manifold conduit interior volume is sufficiently large toinduce a pressurized chlorine dioxide gas stream temperature within saidat least one manifold conduit of less than about 163° F. (73° C.). 5.The chlorine dioxide solution generator of claim 4 wherein said firstand second inlet ports each has an inlet port conduit extendingtherefrom for receiving first and second chlorine dioxide gas streamsfrom said chlorine dioxide gas source, wherein said first and secondoutlet ports each has an outlet port conduit extending therefrom fordischarging first and second pressurized chlorine dioxide gas streams,and wherein said exhaust manifold assembly comprises first and secondmanifold conduits defining an aggregate conduit interior volume fordirecting said first and second pressurized chlorine dioxide gasstreams, respectively, from said gas transfer pump to said absorptionloop, wherein said aggregate manifold conduit interior volume issufficiently large to inhibit chlorine dioxide decomposition in saidpressurized chlorine dioxide gas stream.
 6. The chlorine dioxidesolution generator of claim 5 wherein said outlet port conduits areformed from a material having a melting point greater than about 140° F.(60° C.).
 7. The chlorine dioxide solution generator of claim 6 whereinsaid outlet port conduits are formed from a material selected from thegroup consisting of polytetrafluoroethylene,polychlorotrifluoroethylene, chlorinated poly(vinyl chloride), titaniumand other metals having a melting point greater than about 140° F. (60°C.).
 8. The chlorine dioxide solution generator of claim 4 wherein saidfirst and second inlet ports each has an inlet port conduit extendingtherefrom for receiving first and second chlorine dioxide gas streamsfrom said chlorine dioxide gas source, wherein said first and secondoutlet ports each has a pair of outlet port conduits extending therefromfor discharging two pairs of pressurized chlorine dioxide gas streams,and wherein said exhaust manifold assembly comprises at least onemanifold conduit defining an aggregate conduit interior volume fordirecting said first and second pressurized chlorine dioxide gasstreams, respectively, from said gas transfer pump to said absorptionloop, wherein said aggregate manifold conduit interior volume issufficiently large to inhibit chlorine dioxide decomposition in saidpressurized chlorine dioxide gas stream.
 9. The chlorine dioxidesolution generator of claim 8 wherein said outlet port conduits areformed from a material having a melting point greater than about 140° F.(60° C.).
 10. The chlorine dioxide solution generator of claim 9 whereinsaid outlet port conduits are formed from a material selected from thegroup consisting of polytetrafluoroethylene,polychlorotrifluoroethylene, chlorinated poly(vinyl chloride), titaniumand other metals having a melting point greater than about 140° F. (60°C.).
 11. The chlorine dioxide solution generator of claim 8 wherein saidexhaust manifold assembly comprises a single manifold conduit definingan interior volume for directing said two pairs of pressurized chlorinedioxide gas streams from said gas transfer pump to said absorption loop,wherein said interior volume is sufficiently large to inhibit chlorinedioxide decomposition in said pressurized chlorine dioxide gas stream.12. The chlorine dioxide solution generator of claim 1 wherein a ratioof the cross-sectional diameter of said at least one manifold conduit tothe cross-sectional diameter of said at least one gas transfer pumpoutlet port is greater than
 1. 13. The chlorine dioxide solutiongenerator of claim 1 wherein said exhaust manifold assembly has acoolant fluid stream in thermal contact therewith, whereby said coolantfluid stream further inhibits chlorine dioxide decomposition in saidpressurized chlorine dioxide gas stream.
 14. The chlorine dioxidesolution generator of claim 13 wherein said coolant fluid stream is inthermal contact with said at least one manifold conduit.
 15. Thechlorine dioxide solution generator of claim 14 wherein thermal contactof said coolant fluid stream with said at least one manifold conduitfurther induces a pressurized chlorine dioxide gas stream temperaturewithin said at least one manifold conduit of less than about 163° F.(73° C.).
 16. A method of generating a chlorine dioxide solutioncomprising: (a) providing a source of chlorine dioxide gas; (b)effecting the dissolution of chlorine dioxide into a liquid stream byemploying an absorption loop fluidly connected to said chlorine dioxidegas source; (c) interposing a gas transfer pump between said chlorinedioxide gas source and said absorption loop, said gas transfer pumphaving at least one inlet port for receiving a chlorine dioxide gasstream from said chlorine dioxide gas source and at least one outletport for discharging a pressurized chlorine dioxide gas stream; (d)interposing an exhaust manifold assembly between said gas transfer pumpoutlet port and said absorption loop, said exhaust manifold assemblycomprising at least one manifold conduit defining an interior volume fordirecting said pressurized chlorine dioxide gas stream from said atleast one gas transfer pump outlet port to said absorption loop; and (e)inhibiting chlorine dioxide decomposition in said pressurized chlorinedioxide gas stream by effecting a volumetric increase between said atleast one gas transfer pump outlet port and said at least one manifoldconduit.
 17. The method of claim 16 wherein said volumetric increaseinduces a pressurized chlorine dioxide gas stream temperature withinsaid at least one manifold conduit of less than about 163° F. (73° C.).